Electrochemical method for providing hydrogen using ammonia and ethanol

ABSTRACT

An electrochemical method for providing hydrogen using ammonia, ethanol, or combinations thereof, comprising: forming an anode comprising a layered electrocatalyst, the layered electrocatalyst comprising at least one active metal layer deposited on a carbon support; providing a cathode comprising a conductor; disposing a basic electrolyte between the anode and the cathode; disposing a fuel within the basic electrolyte; and applying a current to the anode causing the oxidation of the fuel, forming hydrogen at the cathode.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims priority to the provisional application having application Ser. No. 60/916,222, to the provisional application having the application Ser. No. 60/974,766, to the PCT application WO/2006/121981, which in turn claims priority to the provisional application having Ser. No. 60/678,725, and to the utility application having the application Ser. No. 10/962,894, which in turn claims priority to the provisional application having Ser. No. 60/510,473, the entirety of which are incorporated herein by reference.

FIELD

The present embodiments relate to an electrochemical method for providing hydrogen using ammonia, ethanol, or combinations thereof.

BACKGROUND

A need exists for an electrochemical method that incorporates use of an electrochemical cell able to oxidize ammonia, ethanol, or combinations thereof in alkaline media continuously.

A further need exists for an electrochemical method that utilizes an electrode having a unique layered electrocatalyst that overcomes the positioning of the electrode due to surface blockage.

A need also exists for an electrochemical method that utilizes a layered electrocatalyst with a carbon support that provides a hard rate of performance for the carbon support.

The present embodiments meet these needs.

BRIEF DESCRIPTION OF THE DRAWINGS

The detailed description will be better understood in conjunction with the accompanying drawings as follows:

FIG. 1 depicts an embodiment of an electrochemical cell useable with the present method.

FIG. 2 depicts an exploded view of an embodiment of the an electrochemical cell stack useable with the present method.

FIG. 3 shows adsorption of OH on a Platinum cluster.

FIG. 4 shows experimental results of the electro-oxidation of ammonia on a Pt electrode, using a rotating disk electrode.

FIG. 5 shows results of microscopic modeling of the electro-adsorption of OH, indicating that if the sites were available, the adsorption of OH would continue producing higher oxidation currents

FIG. 6 shows a representation of the electro-oxidation mechanism of ammonia on a Pt electrode. As NH3 reaches the Pt surface it competes with the OH″ electro-adsorption. Since the Electro-adsorption of OH″ is faster on Pt the active sites of the electrode get saturated with the OH adsorbates causing deactivation of the electrode.

FIG. 7 shows a schematic representation of the procedure used to increase the electronic conductivity of the carbon fibers during plating and operation.

FIG. 8 shows SEM photographs of the carbon fibers before plating and after plating.

FIG. 9 shows cyclic voltammetry performance of 1M Ammonia and 1M KOH solution at 25° C., comparing the performance of the carbon fiber electrodes with different compositions.

FIG. 10 shows cyclic voltammetry performance of 1M Ammonia and 1M KOH solution at 25° C., comparing the loading of the electrode, with low loading 5 mg of total metal/cm of carbon fiber and high loading 10 mg of metal/cm of carbon fiber.

FIG. 11 shows cyclic voltammetry performance of 1M Ammonia and 1M KOH solution at 25° C., comparing differing electrode compositions at low loading of 5 mg of total metal/cm of fiber. Electrode compositions include High Rh, Low Pt (80% Rh, 20% Pt), and low Rh and high Pt (20% Rh, 80% Pt).

FIG. 12 shows cyclic voltammetry performance of 1M Ammonia and 1M KOH solution at 25° C., with differing ammonia concentration, indicating that the concentration of NH3 does not affect the kinetics of the electrode.

FIG. 13 shows cyclic voltammetry performance of Effect of solution at 25° C., with differing OH concentration, indicating that a higher the concentration of OH causes faster kinetics.

FIG. 14 shows cyclic voltammetry performance of 1M ethanol and 1M KOH solution at 25° C., indicating that the present electrochemical cell is also useable for the continuous oxidation of ethanol.

FIG. 15 shows energy (a) and Power balance (b) of an ammonia electrochemical cell, exhibiting a low energy consumption compared to that of a commercial water electrolyzer.

FIG. 16 depicts an embodiment of the steps of the present method.

The present embodiments are detailed below with reference to the listed Figures.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Before explaining the present apparatus in detail, it is to be understood that the apparatus is not limited to the particular embodiments and that it can be practiced or carried out in various ways.

The present embodiments relate to an electrochemical method for providing hydrogen through a reaction from the oxidation of ammonia, ethanol, or combinations thereof.

Conventional hydrogen production is expensive, energy inefficient, and creates unwanted byproducts.

The present electrochemical method provides the benefit of continuous, in-situ generation of hydrogen through the oxidation of ammonia, ethanol, or combinations thereof. The present electrochemical method produces hydrogen through the oxidation of both ammonia and ethanol, with a faradic efficiency of 100%. In both cases, the reaction that takes place at the cathode is the reduction of water in alkaline medium, through the following reaction:

2H₂O+2e ⁻→H₂+2OH⁻E⁰=0.82 V vs SHE

where SHE is a standard hydrogen electrode.

Hydrogen is the main fuel source for power generation using fuel cells, but the effective storage and transportation of hydrogen presents technical challenges. Current hydrogen production costs cause fuel cell technology for distributed power generation to be economically non-competitive when compared to traditional oil-fueled power systems. Current distributed hydrogen technologies are able to produce hydrogen at costs of $5 to $6 per kg of H2. This high production cost is due in part to high product separation/purification costs and high operating temperatures and pressures required for hydrogen production.

Using current technologies, hydrogen can be obtained by the partial oxidation, catalytic steam reforming, or thermal reforming of alcohols and hydrocarbons. However, all of these processes take place at high temperatures and generate a large amount of CO_(X) as byproducts, which must be removed from the hydrogen product. Most of these CO_(X) byproducts cause degeneration of fuel cell performance due to poisoning of the fuel cell catalysts. The removal of these byproducts from the fuel stream is complicated, bulky, and expensive.

Currently, the cleanest way to obtain pure hydrogen is by the electrolysis of water. During the electrolysis of water electrical power (usually provided by solar cells) is used to break the water molecule, producing both pure oxygen and hydrogen. The disadvantage of this process is that a large amount of electrical power is needed to produce hydrogen. The theoretical energy consumption for the oxidation of water is 66 W-h per mole of Ĥ produced (at 25° C.). Therefore, if solar energy is used (at a cost of $0.2138/kWh), the theoretical cost of hydrogen produced by the electrolysis of water is estimated to be $7 per kg of H2.

The present electrochemical method overcomes the costs and difficulties associated with the production of hydrogen, by enabling continuous, controllable evolution of hydrogen through the oxidation of plentiful and inexpensive feedstocks that include ammonia and/or ethanol.

Plating of carbon fibers, nano-tubes, and other carbon supports is a difficult task that is problematic due to the relatively low electronic conductivity of these materials. The low conductivity of carbon supports can cause a poor coating of the surface of the support, which can be easily removed. The electronic conductivity of carbon fibers and other carbon supports decreases along the length from the electrical connection. Therefore, the furthest point of contact to the electric connection transfers a low current when compared with the closest point to the electric contact.

The present electrochemical method advantageously utilizes a unique layered electrocatalyst that provides electrodes with uniform current distribution and enhanced adherence and durability of coating, and overcomes surface coverage affects, leaving a clean active surface area for reaction.

It was believed that surface blockage caused during ammonia electrolysis in alkaline medium was due to the presence of elemental Nitrogen, according to the mechanism proposed by Gerisher:

$2\left( {{{NH}_{3} + M}\underset{k_{1}^{\prime}}{\overset{k_{1}}{\rightleftarrows}}{MNH}_{3}} \right)$ $2\left( {{{MNH}_{3} + {OH}^{-}}\underset{k_{2}^{\prime}}{\overset{k_{2}}{\rightleftarrows}}{{MNH}_{2} + {H_{2}O} + ^{-}}} \right)$ $2\left( {{{MNH}_{2} + {OH}^{-}}\underset{k_{3}^{\prime}}{\overset{k_{3}}{\rightleftarrows}}{{MNH} + {H_{2}O} + ^{-}}} \right)\mspace{11mu} ({rds})$ $\frac{1}{2}\left( {{{MNH} + {MNH}}\underset{k_{4}^{\prime}}{\overset{k_{4}}{\rightleftarrows}}{M_{2}N_{2}H_{2}}} \right)$ $\frac{1}{2}\left( {{{M_{2}N_{2}H_{2}} + {2\; {OH}^{-}}}\underset{k_{5}^{\prime}}{\overset{k_{5}}{\rightleftarrows}}{{M_{2}N_{2}} + {2\; H_{2}O} + {2\; ^{-}}}} \right)$ ${M_{2}N_{2}}\underset{k_{6}^{\prime}}{\overset{k_{6}}{\rightleftarrows}}{N_{2} + {2\; M}}$

Deactivation Reaction:

$2\left( {{{MNH} + {OH}^{-}}\underset{k_{4}^{\prime}}{\overset{k_{4}}{\rightleftarrows}}{{MN} + {H_{2}O} + ^{-}}} \right)$

where M represents an active site on the electrode.

The present electrochemical method incorporates the demonstrations of two independent methods indicating that the proposed mechanism by peripher is not correct, and that OH needs to be adsorbed on the electrode for the reactions to take place. Furthermore, the electrode is deactivated by the OH adsorbed at the active sites.

Results from molecular modeling indicate that the adsorption of OH on an active Pt site is strong (chemisorption) and can be represented by the following reaction:

Pt₁₀+OH⁻

Pt₁₀−OH_((ad)) +e ⁻

FIG. 3 shows a bond between a OH and a platinum cluster. The system was modeled using Density functional Methods. The computations were performed using the B3PW91 and LANL2DZ method and basis set, respectively. The binding energy for the Pt—OH cluster is high with a value of −133.24 Kcal/mol, which confirms the chemisorption of OH on a Pt cluster active site.

Additionally, results from microscopic modeling as well as experimental results on a rotating disk electrode (RDE) indicate that the adsorption of OH is strong and responsible for the deactivation of the catalyst.

FIG. 4 compares the baseline of a KOH solution with the same solution in the presence of OH. The curves indicate that the first oxidation peaks that appear at about −0.7 V vs Hg/HgO electrode had to do with the electro-adsorption of OH.

FIG. 5 shows a comparison of the predicted results (by microscopic modeling) with the experimental results for the electro-adsorption of OH. The results indicate that the model predicts the experimental results fairly well. Furthermore, an expression for the surface blockage due to the adsorption of OH at the surface of the electrode was developed (notice that the active sites for reaction theta decay with the applied potential due to adsorbates). If the surface were clean (see results model without coverage), the electro-adsorption of OH would continue even at higher potentials, and would occur more rapidly.

Compiling the experimental results with the modeling results, the following mechanism for the electro-oxidation of ammonia in alkaline medium is proposed: First the adsorption of OH takes place. As the ammonia molecule approaches the electrode, it is also adsorbed on the surface. Through the oxidation of ammonia, some OH adsorbates are released from the surface in the form of water molecules. However, since the adsoiption of OH is stronger, and the OH ions move faster to the surface of the electrode, they are deactivated, increasing potential. There will be a competition on the electrode between the adsorption of OH and NH3.

The results of the mechanism are summarized on the proposed reactions given below, as well as FIG. 6.

Pt₁₀+OH⁻

Pt₁₀−OH⁻ _((ad))  (1)

2Pt₁₀+2NH₃

2Pt₁₀−NH_(3(ad))  (2)

Pt₁₀−NH_(1(ad))+Pt₁₀−OH⁻ _((ad))

Pt₁₀−NH_(2(ad))+Pt₁₀+H₂O+e ⁻  (3)

Pt₁₀−NH_(2(ad))+Pt₁₀−OH⁻ _((ad))

Pt₁₀−NH_((ad))+Pt₁₀+H₂O+e ⁻  (4, rds)

Pt₁₀−NH_((ad))+Pt₁₀−OH⁻ _((ad))

Pt₁₀−N_((ad))+Pt₁₀+H₂O+e ⁻  (5)

2Pt₁₀−N_((ad))

Pt₁₀−N_(3(ad))+Pt₁₀  (6)

Pt₁₀−NH_(2(ad))

Pt₁₀−N_(2(ad))  (7)

This mechanism can be extended to the electro-oxidation of other chemicals in alkaline solution at low potentials (negative vs. standard hydrogen electrode (SHE)). For example, the mechanism has been extended to the electro-oxidation of ethanol. The proposed mechanism clearly defines the expectations for the design of better electrodes: the materials used should enhance the adsorption of NH3 and/or ethanol, or other chemicals of interest. The proposed mechanism can also enhance the electrolysis of water in alkaline medium. Through a combination of at least two materials, one material more likely to be adsorbed by OH than the other, active sites are left available for the electro-oxidation of the interested chemicals, such as NH₃ and/or ethanol.

Significant current densities can be obtained from the oxidation of ammonia on active metals, but such electrodes are far less reversible than those used by the present electrochemical method. Similar cases occur with the electro-oxidation of ethanol in alkaline medium. Furthermore, the activation of the electrodes is limited by surface coverage. The present electrochemical method overcomes the problems of reversibility as well as deactivation.

The present electrochemical method includes the step of forming an anode that includes a layered electrocatalyst.

The layered electrocatalyst includes at least one active metal layer deposited on a carbon support. The carbon support can be integrated with a conductive metal, such as titanium, tungsten, nickel, stainless steel, or other similar conductive metals.

It is contemplated that the conductive metal integrated with the carbon support can have an inability or reduced ability to bind with metal plating layers used to form the layered electrocatalyst.

Active metal layers can include rhodium, rubidium, iridium, rhenium, platinum, palladium, copper, silver, gold, nickel, iron, or combinations thereof.

The active metal layer is contemplated to have a strong affinity for the oxidation of ammonia, ethanol, or combinations thereof. The second metal layer is contemplated to have a strong affinity for hydroxide. The affinities of the layers enhance the electronic conductivity of the carbon support.

Carbon supports can include carbon fibers, carbon tubes, carbon microtubes, carbon microspheres, carbon sheets, carbon nanotubes, carbon nanofibers, or combinations thereof. For example, groups of carbon nanofibers bound in clusters of 6,000, wound on titanium, nickel, carbon steel, or other similar metals, could be used as a carbon support.

Carbon fibers can include woven or non-woven carbon fibers, that are polymeric or other types of fibers. For example, a bundle of polyacrylonitrile carbon fibers could be used as a carbon support. Solid or hollow nano-sized carbon fibers, having a diameter less than 200 nanometers, can also be useable. Bundles of 6000 or more carbon fibers are contemplated, having an overall diameter up to or exceeding 7 micrometers.

Carbon microspheres can include nano-sized Buckyball supports, such as free standing spheres of carbon atoms having plating on the inside or outside, having a diameter less than 200 nanometers. Crushed and/or graded microspheres created from the grinding or milling of carbon, such as Vulcan 52, are also useable.

Carbon sheets can include carbon paper, such as that made by Toray™, having a thickness of 200 nanometers or less. Useable carbon sheets can be continuous, perforated, or partially perforated. The perforations can have diameters ranging from 1 to 50 nanometers.

Carbon tubes can include any type of carbon tube, such as nano-CAPP or nano-CPT, carbon tubes made by Pyrograf®, or other similar carbon tubes. For example, carbon tubes having a diameter ranging from 100 to 200 nanometers and a length ranging from 3,000 to 100,000 nanometers could be used.

In an embodiment, one or more second metal layers can also be deposited on the carbon support. The second metal layers can include additional active metal layers, or layers of different metals.

The second metal layer can include platinum, iridium, or combinations thereof. The ratio of platinum to iridium can range from 99.99:0.01 to 50:50. In an embodiment, the ratio of platinum can range from 95:5 to 70:30. In other embodiments, the ratio of platinum to iridium can range from 80:20 to 75:25.

Formation of the anode can include using sputtering, electroplating, such as use of a hydrochloric acid bath, vacuum electrodeposition, or combinations thereof, to deposit metal layers on the carbon support.

Each layer can be deposited on the carbon support in a thickness ranging from 10 nanometers to 10 microns. For example, a loading of at least 2 mg/cm for each layer can be provided to a carbon fiber support, while both layers can provide a total loading ranging from 4 mg/cm to 10 mg/cm.

Each layer can wholly or partially cover the carbon support. Each layer can be perforated. Each layer can have regions of varying thickness.

It is contemplated that the thickness and coverage of each layer can be varied to accommodate the oxidation of a specified feedstock. For example, a feedstock having a 1M concentration of ammonia could be oxidized by an electrode having a layer that is 0.5 microns in thickness at a rate of 100 mA/cm̂2.

The strong activity of ammonia and/or ethanol of the electrocatalyst used in the present electrochemical method, even with low ammonia concentrations, is useful in processes for removing ammonia from contaminated effluents. Accordingly, the electrocatalysts described herein can be used to oxidize the ammonia contamination in the contaminated effluent. An electrolytic cell may be prepared which uses at least one electrode comprising the layered electrocatalyst described herein to oxidize ammonia contaminants in effluents. The effluent may be fed as a continuous stream, wherein the ammonia is electrochemically removed from the effluent, and the purified effluent is released or stored for other uses.

A cathode that includes a conductor is also provided. The cathode can include carbon, platinum, rhenium, palladium, nickel, Raney Nickel, iridium, vanadium, cobalt, iron, ruthenium, molybdenum, or combinations thereof.

A basic electrolyte is disposed between the anode and the cathode. The basic electrolyte can include any alkaline electrolyte that is compatible with the layered electrocatalyst, does not react with ammonia or ethanol, and has a high conductivity.

The basic electrolyte can include any hydroxide donor, such as inorganic hydroxides, alkaline metal hydroxides, or alkaline earth metal hydroxides. In an embodiment the basic electrolyte can include potassium hydroxide, sodium hydroxide, or combinations thereof.

The basic electrolyte can have a concentration ranging from 0.1 M to 7M. In an embodiment, the basic electrolyte can have a concentration ranging from 3M to 7M.

A fuel is disposed within the basic electrolyte. The fuel can include ammonia, ethanol, or combinations thereof. In an embodiment, the ammonia, ethanol, or combinations thereof can have a concentration ranging from 0.01 M to 5M. In other embodiments, the concentration of ammonia, ethanol, or combinations thereof, can range from 1M to 2M.

The present electrochemical method is useable with only trace amounts of ammonia and/or ethanol. Further, the present electrochemical method is useable with ammonia and/or ethanol individually or simultaneously, thereby enabling the present method to accommodate a large variety of feedstocks.

An electric current is then applied to the anode, such as through use of a power generation system, solar panels, alternate or direct current sources, wind power sources, fuel cells, batteries, other similar power sources, or combinations thereof, causing oxidation of the fuel, forming hydrogen at the cathode. The electric current or current density can be controlled, such as by using controller, to control the output of hydrogen.

In an embodiment, the present electrochemical method can include regulating the electric current to maintain the voltage of the reaction below one volt.

The present electrochemical method can also include placing a membrane or separator between the anode and cathode. The membrane/separator can be selectively permeable to hydroxide and can include polypropylene, Teflon or other polyamides, fuel-cell grade asbestos, other similar polymers, or combinations thereof.

The present embodiments also relate to a method for surface buffered, assisted electrolysis of water, which is also useable to produce hydrogen.

An anode is formed, having a layered electrocatalyst, as described previously. The layered catalyst includes both an active metal layer and at least a second metal layer deposited on a carbon support. A cathode that includes a conductor is also provided.

An aqueous basic electrolyte, that includes water, is disposed between the anode and the cathode.

A buffer solution is disposed within the aqueous basic electrolyte. The buffer solution can include ammonia, ethanol, propanol, or combinations thereof. The concentration of the buffer solution can range from 1 ppm to 100 ppm. It is contemplated that only trace amounts of the buffer solution are necessary to assist the electrolysis of the water.

An electric current is then applied to the anode, causing oxidation of the water within the aqueous basic electrolyte, forming hydrogen at the cathode.

The electric current can be controlled to regulate the hydrogen output. It is also contemplated that the electric current can be regulated to maintain a voltage of one volt or less.

The present embodiments further relate to a method for open circuit electrolysis of water.

An anode is formed, having a layered electrocatalyst, as described previously. The layered catalyst includes both an active metal layer and at least a second metal layer deposited on a carbon support. A cathode that includes a conductor is also provided.

An aqueous basic electrolyte that includes water is disposed between the anode and cathode.

A buffer solution, which can include trace quantities of ammonia, ethanol, propanol, or combinations thereof, as described previously, is then disposed within the aqueous basic electrolyte.

The addition of the buffer solution, in the presence of the basic electrolyte and differing metals of the layered electrocatalyst, causes oxidation of the basic electrolyte to produce hydrogen at the cathode, while producing water at the anode.

The present electrochemical method contemplates use of an electrochemical cell that incorporates the described layered electrocatalyst.

The electrochemical cell includes a first electrode formed from the layered electrocatalyst.

The layered electrocatalyst includes at least one active metal layer deposited on a carbon support. In an embodiment, the layered electrocatalyst can further include at least one second metal layer deposited on the carbon support.

In a contemplated embodiment, the second metal layer can be a second layer of an active metal, such that the layered electrocatalyst includes two active metal layers deposited on the carbon support. The thickness of each metal layer can be varied.

The present electrochemical cell can thereby be customized to meet the needs of users. For example, a first user may need to generate hydrogen for fuel from the rapid oxidation of ethanol, while a second user may need to remove ammonia from a fixed volume of water for purification purposes.

FIG. 7 shows a schematic representation of the procedure used to increase the electronic conductivity of the carbon fibers during plating (and also during the operation of the electrode). The fibers were wrapped on a titanium gauze, and were therefore. in electric contact with the metal at different points. This improvement allowed an easy and homogenous plating of the fibers at any point. The electronic conductivity at any point in the fiber was the same as the electronic conductivity of the Ti gauze.

The schematic for the construction of the electrode is also shown in FIG. 7. The plating procedure can include two steps: 1. First layer plating and 2. Second layer plating.

First layer plating includes plating the carbon support with materials that show a strong affinity for OH. Examples include, but are not limited to Rh, Ru, Ni, and Pd. In one preferred embodiment, Rh is used. The first layer coverage should completely plate the carbon support. In some embodiments, the first layer coverage is at least 2 mg/cm of carbon fiber to guarantee a complete plating of the carbon support. In other embodiments, the first layer coverage can be 2.5 mg/cm, 3.0 mg/cm, 3.5 mg/cm, or more.

Second layer plating includes plating the electrode with materials that have a strong affinity for the oxidation of ammonia and/or ethanol. Examples include: Pt and Ir. Monometallic deposition and/or bimetallic deposition of these materials can be performed. Ratios of Pt:Ir can range from 100% Pt-0% Ir to 50% Pt-50% Ir.

Table I summarizes the plating conditions for the anode and the cathode of the electrochemical cell. After plating the Rhodium, the electrode is weighted. The weight corresponds to the Rhodium loading. Then, the Platinum is deposited on top of the Rhodium. After the procedure is completed, the electrode is measured again. The measurement will correspond to the total loading. The Platinum loading is obtained by subtracting the total loading from the previous Rhodium measurement. The relation of Platinum to Rhodium is then calculated as the percentage of fixed loading. Because the loading depends on the length of the fiber, another measurement should be calculated. It is known that 10 cm of fiber weights 39.1 mg, and because the weight of the fiber is known, then by proportionality, it can be known the length of the total fiber that is being used in each electrode.

Table II summarizes the general conditions of a plating bath useable to create the electrodes. During the entire plating procedure, the solution was mixed to enhance the transport of the species to the carbon support.

Table III shows examples of some electrode compositions, lengths, and loadings of active metals.

TABLE 1 Conditions for Electro-plating Technique in the Deposition of Different Metals on the Carbon Fibers and/or Carbon Nanotubes Metal Plated Rhodium (Rh) Platinum (Pt) Nickel (Ni) Position on the First Second First Electrode Surface: Geometry: 2 × 2 cm² 2 × 2 cm² 4 × 4 cm² Conditions of the Total Volume: 250 ml Total Volume: 250 ml Total Volume: 500 ml Solution: Composition of the 1M HC1 + Rhodium (III) 1M HC1 + Hydrogen Watt's Bath: Solution: Chloride (RhCl₃•XH₂O). Rh Hexachloroplatinate (IV) Nickel Sulphate (NiS0₄••6H₂0) 38.5-45.5% (different Hydrate, 99.9% 280 g/L Nickel Chloride compositions, depending on (H₂PtCl₆•6H₂O) (different (NiCl₂•6H₂O) 40 g/L Boric Acid loadings) compositions, depending (H₃BO₃) 30 g/L on loadings) Counter Electrode: Double Platinum Foil Purity Double Platinum Foil Nickel Spheres (6 to 16 mm p.a.) 99.95% 20 × 50 × (0.004″) Purity 99.95% in contact with a Nickel Foil 20 × 50 × (0.004″) Electrode 99.9+% Purity (0.125 mm thick) Temperature: 70° C. 70° C. 45° C. Time: See Applied Current See Applied Current 8 h approximately Loading: 5 mg/cm of Fiber 5 mg/cm of Fiber Fixed Parameter, Between 6-8 mg/length of fiber Applied Current: 100 mA (30 min) + 120 mA 40 mA (10 min) 4-60 (10 Stairs from 100 mA, to 120 mA (30-60 min), depending on min) H-80 mA (10 min) 4- and then to 140 mA loading 100 mA (1-2 h), depending on loading

TABLE 2 General Conditions of the Plating Bath Pretreatment Degreasing using acetone Bath Type Chloride salts in HC1 Solution Composition Metal/metal ratios varied for optimum deposit composition Applied Current Galvanostatic (1 to 200 mA) Deposition Time Varied from 30 minutes to several hours

TABLE 3 Examples of some Electrode Compositions and Loadings Ratio Total Length, ID Composition Pt:Rh Loading, mg cm Mg/cm 2x2-1 21%Rh—79%Pt 3.81 252.5 30.0 8.4 2x2-2 30%Rh—70%Pt 2.31 146.0 33.4 4.4 2x2-3 23%Rh—73%Pt 3.44 151.5 30.5 5.0 2x2-4 30%Rh—70%Pt 2.32 308.8 31.3 9.9 2x2-5 Rh—Ir—Pt 1.36 196.4 38.0 5.2 2x2-6 80%Rh—20%Pt 0.25 169.9 33.3 5.1 2x2-7 100%Rh — 157.0 31.6 5.0 2x2-8 30%Rh—70%Pt 2.30 160.6 30.9 5.2 2x2-9 100%Pt — 161.9 32.3 5.0

FIG. 8 shows a Scanning Electron Microscope photograph of the electrode before plating and after plating. A first layer of Rh was deposited on the electrode to increase the electronic conductivity of the fibers and to serve as a free substrate for the adsorption of OH. (OH has more affinity for Rh than for Pt). A second layer consisting of Pt was plated on the electrode. The Pt layer did not cover all the Rh sites, leaving the Rh surface to act as a preferred OH adsorbent.

FIG. 9 shows the cyclic voltammetry performance for the electro-oxidation of ammonia on different electrode compositions. Notice that the carbon fibers plated with only Rh are not active for the reaction, while when they are plated with only Pt, the electrode is active but it is victim of poisoning. On the other hand, when the electrode is made by plating in layers: first Rh is deposited and then a second layer consisting of Pt is deposited, the electrode keeps the activity. This is explained by the mechanism presented previously. FIG. 9 demonstrates that the proposed method or preparation of the electrode eliminates surface blockage difficulties.

FIG. 10 shows the effect of different total loading on the electro-oxidation of ammonia. The results indicate that the catalyst with the lowest loading is more efficient for the electro-oxidation of ammonia. This feature results in a more economical process owing to a lower expense related to the catalyst. Additional loading of the catalyst just causes the formation of layers over layers that do not take part in the reaction.

FIG. 11 illustrates the effect of the catalyst composition of the electro-oxidation of ammonia in alkaline solution. There is not a notable difference in the performance of the electrode due to the composition of the electrode. This lack of difference is due to the fact that as long as a first layer of Rh is plated on the electrode, surface blockage will be avoided. Additional plating of Pt would cause the growth of a Pt island (see SEM picture, FIG. 8), which is not completely active in the whole surface.

FIG. 12 shows the effect of ammonia concentration on the performance of the electrode. The effect of ammonia concentration is negligible on the electrode performance. This is due to the fact that the active Pt sites have already adsorbed the NH3 needed for a continuous reaction. Due to this feature, the present electrochemical cell is operable using only trace amounts of ammonia and/or ethanol.

FIG. 13 depicts the effect of the concentration of OH on the electro-oxidation of ammonia. A larger concentration of OH causes a faster rate of reaction. The electrode maintains continuous activity, without poisoning, independent of the OH concentration.

FIG. 14 shows the evaluation of the electrode for the electro-oxidation of ethanol. Continuous electro-oxidation of ethanol in alkaline medium is achieved without surface blockage. The present electrochemical cell is thereby useable to oxidize ethanol, as well as ammonia. The present electrochemical cell can further oxidize combinations of ammonia and ethanol independently or simultaneously.

In an embodiment, the second electrode and first electrode can both include a layered electrocatalyst.

The second electrode is contemplated to have an activity toward the evolution of hydrogen an alkaline media.

The first electrode, second electrode, or combinations thereof, can include rotating disc electrodes, rotating ring electrodes, cylinder electrodes, spinning electrodes, ultrasound vibration electrodes, other similar types of electrodes, or combinations thereof.

The electrochemical cell further includes a basic electrolyte disposed in contact with each of the electrodes.

It is contemplated that the basic electrolyte can be present in a volume and/or concentration that exceeds the stoichiometric proportions of the oxidation reaction, such as two to five times greater than the concentration of ammonia, ethanol, or combinations thereof. In an embodiment, the basic electrolyte can have a concentration three times greater than the amount of ammonia and/or ethanol.

The electrochemical cell can include ammonia, ethanol, or combinations thereof, which can be supplied as a fuel/feedstock for oxidation to produce hydrogen.

The electrochemical cell can advantageously oxidize any combination of ammonia or ethanol, independently or simultaneously. A feedstock containing either ammonia, ethanol, or both ammonia and ethanol could be thereby be oxidized using the present electrochemical cell. Additionally, separate feedstocks containing ammonia and ethanol could be individually or simultaneously oxidized using the electrochemical cell.

The ammonia, ethanol, or combinations thereof can be present in extremely small, millimolar concentrations, while still enabling the electrochemical cell to be useable.

The ammonia and/or ethanol can be aqueous, having water, the basic electrolyte, or another liquid as a carrier. For example, ammonium hydroxide can be stored until ready for use, then fed directly into the electrochemical cell.

It is also contemplated that ammonia can be stored as liquefied gas, at a high pressure, then combined with water and the basic electrolyte when ready for use. Ammonia could also be obtained from ammonium salts, such as ammonium sulfate, dissolved in the basic electrolyte.

In an embodiment, the ammonia, ethanol, or combinations thereof can have a concentration ranging from 0.01 M to 5M. In other embodiments, the concentration of ammonia, ethanol, or combinations thereof, can range from 1M to 2M. At higher temperatures, a greater concentration of ammonia can be used.

The properties of the electrochemical cell, such as the thickness of the plating of the first electrode, can be varied to accommodate the concentration of the feedstock.

The ability of the electrochemical cell to perform oxidation of extremely small, millimolar concentrations of ammonia and/or ethanol enables the electrochemical cell to advantageously be used as a detector/sensor for ammonia and/or ethanol.

The ability of the electrochemical cell to perform oxidation of both extremely small and large concentrations of ammonia and/or ethanol enables the electrochemical cell to advantageously accommodate a large variety of feedstocks.

The oxidation of ammonia and/or ethanol by the electrochemical cell is endothermic. As a result, the electrochemical cell can be used to cool other adjacent or attached devices and equipment, such as a charging battery. Additionally, the heat from the adjacent devices and/or equipment can facilitate the efficiency of the reaction of the electrochemical cell, creating a beneficial, synergistic effect.

The electrical current supplied to the electrochemical cell can vary depending on the properties of the cell and/or feedstock, based on the Faraday equation.

Contemplated current densities can range from 25 mA/cm̂2 to 500 mA/cm̂2. In other embodiments, the current densities can range from 50 mA/cm̂2 to 100 mA/cm̂2. In still other embodiments, the current densities can range from 25 mA/cm̂2 to 50 mA/cm̂2. Current densities can also range from 50 mA/cm̂2 to 500 mA/cm̂2, from 100 mA/cm̂2 to 400 mA/cm̂2, or from 200 mA/cm̂2 to 300 mA/cm̂2.

The electrical current can be provided from a power generation system, specifically designed to oxidize ammonia and/or ethanol. The power generation system is contemplated to be adjustable to large current, while providing power of one volt or less.

When electrical current is supplied to the electrochemical cell, it is contemplated that the electrochemical cell can produce hydrogen, nitrogen, carbon dioxide, or combinations thereof. A controlled ammonia feedstock reacts, in the alkaline medium, in combination with the controlled voltage and current, to produce nitrogen and hydrogen. A controlled ethanol feedstock reacts similarly, to produce carbon dioxide and hydrogen.

The electrochemical cell is contemplated to be operable at temperatures ranging from −50 degrees Centigrade to 200 degrees Centigrade. In an embodiment, the cell can be operable from 20 degrees Centigrade to 70 degrees Centigrade. In another embodiment, the cell is operable from 60 degrees Centigrade to 70 degrees Centigrade.

The cell can also be operable from 20 degrees Centigrade to 60 degrees Centigrade, from 30 degrees Centigrade to 70 degrees Centigrade, from 30 degrees Centigrade to 60 degrees Centigrade, or from 40 degrees Centigrade to 50 degrees Centigrade.

It is contemplated that in an embodiment, a higher pressure can be used, enabling the electrochemical cell to be operable at higher temperatures.

The electrochemical cell is contemplated to be useable at pressures ranging from less than 1 atm to 10 atm.

A prototype system for the continuous electrolysis of ammonia and/or ethanol in alkaline medium produced H2 continuously, with a faradic efficiency of 100%. The design of the cell was small (4×4 cm), and permitted a significant production of H₂ at a small energy and power consumption. A cloud of H₂ was observed when generated at the cathode of the cell. The production of H₂ was massive, which demonstrates the use of the cell for in-situ H₂ production.

FIG. 15 shows the energy balance and the power balance on the ammonia electrolytic cell. The electrochemical cell outperforms a commercial water electrolyzer. Both the energy and the power balance of the cell indicate that the cell could operate by utilizing some energy produced by a PEM H₂ fuel cell, and the system (ammonia electrolytic cell/PEM fuel cell) will still provide some net energy. This arrangement can be used to minimize hydrogen storage.

In one exemplary system, an excess of 480 kg of H₂ was produced per day. A total capital investment of $1,000,000 is needed for the construction of the power system. A comparison of the economic analysis for the production of H₂ using the ammonia continuous electrolytic cell with current state of the art technologies (natural gas reforming and water electrolysis) for distributed power has been performed. The continuous ammonia electrolyzer can produce hydrogen at less than $2 per Kg. Compared to other technologies for in situ hydrogen production, savings are substantial—using numbers provided by the National Academy of Science, the continuous ammonia electrolyzer produced H2 about 20% cheaper than H2 can be produced using natural gas steam reforming, and about 57% cheaper than using water electrolysis.

The electrochemical cell can be used to form one or more electrochemical cell stacks, useable with the present electrochemical method, by connecting a plurality of electrochemical cells in series, parallel, or combinations thereof.

The electrochemical cell stack can include one or more bipolar plates disposed between at least two adjacent electrochemical cells. The bipolar plate can include an anode electrode, a cathode electrode, or combinations thereof. For example, the bipolar plate could function as an anode for both adjacent cells, or the bipolar plate could have anode electrode materials deposited on a first side and cathode electrode materials deposited on a second side.

The electrochemical cell stack can have any geometry, as needed, to facilitate stacking, storage, and/or placement. Cylindrical, prismatic, spiral, tubular, and other similar geometries are contemplated.

In an embodiment, a single cathode electrode can be used as a cathode for multiple electrochemical cells within the stack, each cell having an anode electrode.

In this embodiment, at least a first electrochemical cell would include a first electrode having a layered electrocatalyst, as described previously, and a second electrode having a conductor.

At least a second of the electrochemical cells would then have a third electrode that includes the layered electrocatalyst. The second electrode would function as the cathode for both the first and the second electrochemical cells.

In a contemplated embodiment, an electrochemical cell stack having a plurality of anode electrodes having the layered electrocatalyst and a single cathode having a conductor can be used. For example, multiple disc-shaped anode electrodes can be placed in a stacked configuration, having single cathode electrode protruding through a central hole in each anode electrode.

A basic electrolyte and ammonia, ethanol, or combinations thereof can then be placed in contact with each of the plurality of anode electrodes and with the cathode electrode.

It is contemplated that this embodiment of the electrochemical cell stack can include a hydrogen-permeable membrane for facilitating collection of the hydrogen produced by the electrochemical cell stack.

The described embodiment of the electrochemical cell stack can further have a fuel and current inlet in communication with each of the plurality of anodes, simultaneously, such as by extending through the central hole of each of the anodes.

Referring now to FIG. 1, FIG. 1 depicts a diagram of the components of an electrochemical cell (10) useable with the present electrochemical method.

The electrochemical cell (10) is depicted having a first electrode (11), which functions as an anode. The first electrode (11) is shown having a layered electrocatalyst (12) deposited on a carbon support (26). The layered electrocatalyst (12) is contemplated to include at least one active metal layer and can include at least one second metal layer.

The electrochemical cell (10) further depicts a second electrode (13) which is contemplated to include a conductor.

The electrodes (11, 13) are disposed within a housing (5), such that a space exists between the electrodes (11, 13).

The electrochemical cell (10) is shown containing a basic electrolyte (36), such as sodium hydroxide or potassium hydroxide. The electrochemical cell (10) is also shown containing ammonia (20) and ethanol (22) within the basic electrolyte (36). It is contemplated that the electrochemical cell (10) is useable for the continuous oxidation of ammonia or ethanol individually, or simultaneously.

Electrical current (34) from a power generation system (7) in communication with the electrodes (11, 13) is applied to the first electrode (11) to cause the production of hydrogen (32) through the oxidation of the ammonia (20) and/or ethanol (22).

The depicted electrochemical cell (10) is shown having a hydrophilic membrane (9) disposed between the electrodes (11, 13), which is contemplated to selectively permit hydroxide exchange.

Referring now to FIG. 2, a diagram of an embodiment of an electrochemical cell stack (16) useable with the present method is shown. The electrochemical cell stack (16) is shown having two of electrochemical cells, separated by a bipolar plate (3), which are depicted in greater detail in FIG. 1.

The electrochemical cell stack (16) includes a first anode (11 a) adjacent a first end plate (92 a). A first gasket (94 a) and a second gasket (94 b) are disposed between the first anode (11 a) and the bipolar plate (3).

The electrochemical cell stack (16) also includes a second anode (11 b) adjacent a second endplate (92 b) opposite the first end plate (92 a). A third gasket (94 c) and a fourth gasket (94 d) are disposed between the second anode (11 b) and the bipolar plate (3).

The bipolar plate includes a cathode (13) disposed thereon. The cathode (13) is contemplated to function as a cathode for both the first anode (11 a) and the second anode (11 b).

While FIG. 2 depicts the electrochemical cell stack (16) including two electrochemical cells, it should be understood that any number of electrochemical cells, such as five cells or nine cells, can be stacked in a similar fashion, to produce a desired volume of hydrogen.

Referring now to FIG. 16, a diagram of an embodiment of the present electrochemical method is shown.

FIG. 16 depicts that an anode is formed by combining one or more active metal layers and, optionally, a second metal layer, with a carbon support, such as by electrodeposition. (100). A cathode having a conductor is provided (102).

A basic electrolyte is disposed between the anode and cathode (104). A fuel is also provided within the basic electrolyte (106).

A current is then applied to the anode, such as through connection with a power source, causing oxidation of the fuel, forming hydrogen at the cathode (108).

While these embodiments have been described with emphasis on the embodiments, it should be understood that within the scope of the appended claims, the embodiments might be practiced other than as specifically described herein. 

1. An electrochemical method for producing hydrogen by applying an electric current to ammonia, ethanol, or combinations thereof, causing a reaction, the method comprising: forming an anode comprising a layered electrocatalyst, wherein the layered electrocatalyst comprises a carbon support integrated with a conductive metal; and at least one active metal layer at least partially deposited on the carbon support, wherein the at least one active metal layer is active to ethanol, ammonia, or combinations thereof, and wherein the at least one active metal layer has a thickness ranging from 10 nanometers to 10 microns; providing a cathode comprising a conductor; disposing a basic electrolyte between the anode and the cathode; flowing a fuel to the basic electrolyte; applying an electric current to the anode causing oxidation of the fuel, evolving hydrogen at the cathode.
 2. The electrochemical method of claim 1, wherein the fuel is flowed continuously to the basic electrolyte.
 3. The electrochemical method of claim 1, wherein the layered electrocatalyst further comprises at least one second metal layer deposited on the carbon support, wherein the at least one second metal layer is active to OH adsorption and inactive to the target species, and wherein the at least one second metal plating layer has a thickness ranging from 10 nanometers to 10 microns.
 4. The electrochemical method of claim 1, further comprising the step of controlling the electric current to control the output of the hydrogen.
 5. The electrochemical method of claim 1, further comprising the step of regulating the electric current to maintain a voltage below one volt.
 6. The electrochemical method of claim 1, wherein the step of forming the anode comprises using sputtering, electroplating, vacuum electrodeposition, or combinations thereof to deposit the at least one active metal layer on the carbon support.
 7. The electrochemical method of claim 1, wherein the fuel comprises ammonia, ethanol, or combinations thereof.
 8. The electrochemical method of claim 1, wherein the at least one active metal layer comprises rhodium, rubidium, iridium, rhenium, platinum, palladium, copper, silver, gold, nickel, iron, or combinations thereof.
 9. The electrochemical method of claim 1, wherein the cathode comprises carbon, platinum, rhenium, palladium, nickel, iridium, vanadium, cobalt, iron, ruthenium, molybdenum, or combinations thereof.
 10. The electrochemical method of claim 1, further comprising placing a membrane or separator between the anode and the cathode.
 11. The electrochemical method of claim 1, wherein the electric current is provided using a power generation system, a solar panel, an AC power source, a DC power source, a wind power source, a fuel cell, a battery, other similar power sources, or combinations thereof.
 12. A method for surface buffered, assisted electrolysis of water, the method comprising: forming an anode comprising a layered electrocatalyst, wherein the layered electrocatalyst comprises: a carbon support integrated with a conductive metal; at least one active metal layer at least partially deposited on the carbon support, wherein the at least one active metal layer is active to a target species, and wherein the at least one active metal layer has a thickness ranging from 10 nanometers to 10 microns; and at least one second metal layer deposited on the at least one active metal layer, wherein the at least one second metal layer is active to OH adsorption and inactive to the target species, and wherein the at least one second metal plating layer has a thickness ranging from 10 nanometers to 10 microns; providing a cathode comprising a conductor; disposing an aqueous basic electrolyte comprising water between the anode and the cathode; disposing a buffer solution within the aqueous basic electrolyte; and applying an electric current to the anode causing oxidation of the water, evolving hydrogen at the cathode.
 13. The method of claim 12, wherein the buffer solution comprises ammonia, ethanol, propanol, or combinations thereof.
 14. The method of claim 13, wherein the buffer solution has a concentration ranging from 1 ppm to 100 ppm.
 15. The method of claim 12, further comprising the step of controlling the electric current to control the rate at which the hydrogen is evolved at the cathode.
 16. The method of claim 12, further comprising the step of regulating the electric current to maintain a voltage below one volt.
 17. A method for open circuit electrolysis of water, the method comprising: forming an anode comprising a layered electrocatalyst, wherein the layered electrocatalyst comprises: a carbon support integrated with a conductive metal; at least one active metal layer at least partially deposited on the carbon support, wherein the at least one active metal layer is active to a target species, and wherein the at least one active metal layer has a thickness ranging from 10 nanometers to 10 microns; and at least one second metal layer deposited on the at least one active metal layer, wherein the at least one second metal layer is active to OH adsorption and inactive to the target species, and wherein the at least one second metal plating layer has a thickness ranging from 10 nanometers to 10 microns; providing a cathode comprising a conductor; disposing an aqueous basic electrolyte comprising water between the anode and the cathode; disposing a buffer solution within the aqueous basic electrolyte, thereby causing oxidation of the basic electrolyte to evolve hydrogen at the cathode while producing water at the anode.
 18. The method of claim 17, wherein the buffer solution comprises ammonia, ethanol, propanol, or combinations thereof.
 19. The method of claim 17, wherein the buffer solution has a concentration ranging from 1 ppm to 100 ppm. 